Experimental Evidence for Nonthermal Contributions to Plasmon-Enhanced Electrochemical Oxidation Reactions

Photocatalysis based on plasmonic nanoparticles has emerged as a promising approach to facilitate light-driven reactions under far milder conditions than thermal catalysis. Several effects, such as strong local electromagnetic fields, increased electron and lattice temperatures, or the transfer of nonthermal charge carriers, could contribute to the reaction rate enhancement. In order to understand plasmon-enhanced catalysis and to enable plasmonic platforms, a distinction between the different underlying effects is required. We investigate the electrochemical model reactions oxidative hydroxide adsorption and glucose oxidation and deconvolve the enhancement processes via their dependence on the excitation wavelength. We observe that nonthermal effects contribute significantly to the plasmonic enhancement.